EP1149151B1 - Low-density compositions and particulates including same - Google Patents

Low-density compositions and particulates including same Download PDF

Info

Publication number
EP1149151B1
EP1149151B1 EP00903190A EP00903190A EP1149151B1 EP 1149151 B1 EP1149151 B1 EP 1149151B1 EP 00903190 A EP00903190 A EP 00903190A EP 00903190 A EP00903190 A EP 00903190A EP 1149151 B1 EP1149151 B1 EP 1149151B1
Authority
EP
European Patent Office
Prior art keywords
low
density
enzyme
porous
granules
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP00903190A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1149151A2 (en
Inventor
Robert I. Christensen, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Danisco US Inc
Original Assignee
Genencor International Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=22360201&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1149151(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Genencor International Inc filed Critical Genencor International Inc
Publication of EP1149151A2 publication Critical patent/EP1149151A2/en
Application granted granted Critical
Publication of EP1149151B1 publication Critical patent/EP1149151B1/en
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof

Definitions

  • the present invention relates to low-density compositions, as well as particulates formed, at least in part, from such compositions. More particularly, the present invention provides low-density compositions including a non-porous or minimally porous, low-density material. Particulates formed from the low-density compositions of the invention are especially useful as cores for enzyme granules.
  • proteins such as pharmaceutically important proteins, e.g., hormones, and industrially important proteins, e.g., enzymes
  • enzyme granules which have additional beneficial or improved characteristics.
  • enzyme granules for dry (e.g., powdered) detergent formulations have become widely known and extensively developed (as exemplified above), few, if any, granule formulations are available which are suitable for incorporation in liquid detergents.
  • formulators of enzyme granules for liquid detergents must address concerns much like those encountered with dry detergent formulations. It should be appreciated, however, that a liquid-detergent environment presents a variety of challenges of its own. Some of these considerations are discussed next.
  • enzyme granules should be capable of providing sufficient enzyme activity in the wash. It is also generally desirable to have granule with a relatively fast release profile.
  • the enzyme load for each granule needs to be protected from the various harsh components of the liquid formulation (e.g., peroxygen bleaches, such as sodium perborate or sodium percarbonate, and the like), yet the means of achieving such protection must not unduly hinder enzyme release. As is well known by those working in the field, it is often problematic to simultaneously provide good protection for the enzyme and a fast release profile.
  • liquid detergent formulations one problem with the use of particles (which would include enzyme granules) in liquids is that there is a tendency for such products to phase separate as dispersed insoluble solid particulate material drops from suspension and settles at the bottom of the container holding the liquid detergent product.
  • Phase stabilizers such as thickeners or viscosity control agents can be added to such products to enhance the physical stability thereof.
  • Such materials can add cost and bulk to the product without contributing to the laundering/cleaning performance of such detergent compositions.
  • the known enzyme granules are generally unsuitable for use in typical liquid detergents as such granules generally have an unacceptably high density (e.g., 1.45 g/cm 3 , or higher) which would cause them to drop out of suspension in a relatively short period of time (i.e., much less than the typical product shelf life).
  • an unacceptably high density e.g., 1.45 g/cm 3 , or higher
  • a further problem associated with particles in liquids is that it has been observed that the particles can induce visual inhomogeneities in the final product. This represents a problem, as composition aesthetics is a key element in terms of consumer acceptance.
  • Preferred particulate compositions and granules of the present invention are characterized by one or more of the following desirable features: they have a true density less than 1.4 g/cm 3 ; they exhibit sufficient enzyme activity in the wash; they have a relatively fast enzyme-release profile; they have relatively low susceptibility to attritional breakdown; they tend to remain dispersed and suspended in the liquid detergent or cleaner during storage and use (e.g., for at least 3 weeks, and preferably for at least 4 weeks); they have sufficient retained activity in storage; they provide an acceptable (pleasing) visual appearance.
  • the present invention provides exemplary methods of producing such granules, e.g., by way of a marumerization, drum granulation, fluid-bed spray-coating, pan-coating process, or other suitable process.
  • One aspect of the present invention provides a low-density composition including a non-porous or minimally porous, low-density material selected from the group consisting of hollowspheres, aluminum palmitate, aluminum tristearate, lithium borohydride, potassium borohydride, saw dust, milled corncob, aerogel shards, hollow fibers, and low-density forms of silicon dioxide used as flow aids for powders; a binder or binder system (e.g. sucrose); and one or more enzymes (e.g. a hydrolytic enzyme, such as a protease, amylase, cellulase, lipase, esterases and/or peptidase), the composition having a specific gravity of no greater than 1.2 g/cm 3 .
  • a hydrolytic enzyme such as a protease, amylase, cellulase, lipase, esterases and/or peptidase
  • the non-porous or minimally porous, low-density material is comprised of hollowspheres (e.g., borosilicate glass hollowspheres, fused glass hollowspheres, ceramic hollowspheres, plastic hollowspheres, or the like).
  • hollowspheres e.g., borosilicate glass hollowspheres, fused glass hollowspheres, ceramic hollowspheres, plastic hollowspheres, or the like.
  • Q-cel One particularly preferred type of hollowsphere is available commercially under the tradename Q-cel, from PQ Corporation.
  • the low-density composition of the invention has a specific gravity within a range of between 0.95 and 1.15 g/cm 3 .
  • the enzyme-carrying core comprises (i) a low-density composition including (a) a non-porous or minimally porous, low-density material selected from the group consisting of hollowspheres, aluminum palmitate, aluminum tristearate, lithium borohydride, potassium borohydride, saw dust, milled corncob, aerogel shards, hollow fibers, and low-density forms of silicon dioxide used as flow aids for powders and (b) a binder or binder system; and (ii) an enzyme enrobing said composition, the composition having a specific gravity of no greater than 1.2 g/cm 3 .
  • the non-porous or minimally porous, low-density material is comprised of hollowspheres (e.g., Q-cel, from PQ Corporation).
  • the enzyme-carrying core of the invention can be substantially free of enzymes therein (i.e., it can be a non-enzyme containg core); or the core can contain one or more enzymes.
  • the core is a non-enzyme containing core, which can be coated with one or more enzymes, as desired.
  • the enzyme-carrying core of the invention has a specific gravity within a range of between 0.95 and 1.15 g/cm 3 .
  • the present invention provides a low density enzyme granule.
  • the granule comprises (i) a core formed of a low-density composition including a non-porous or minimally porous, low-density material selected from the group consisting of hollowspheres, aluminum palmitate, aluminum tristearate, lithium borohydride, potassium borohydride, saw dust, milled corncob, aerogel shards, hollow fibers, and low-density forms of silicon dioxide used as flow aids for powders; (ii) one or more enzymes; and (iii) an outer coating, the composition having a specific gravity of no greater than 1.2 g/cm 3 .
  • the non-porous or minimally porous, low-density material is comprised of hollowspheres (e.g., borosilicate glass hollowspheres).
  • the granules of the present invention have a specific gravity within a range of between about 0.95 and 1.15 g/cm 3.
  • Still a further aspect of the present invention provides a method for making a low-density granule.
  • the method includes the steps of:
  • the method can further involve overcoating the particulates with a cosmetic coating (e.g., HPMC, PEG, and TiO 2 ).
  • a cosmetic coating e.g., HPMC, PEG, and TiO 2 .
  • granules of the present invention are formed by carrying out the steps of:
  • the low-density material is comprised of hollowspheres (e.g., Q-cel, from PQ Corporation).
  • the present invention provides low-density compositions, as well as particulates formed, at least in part, from such compositions.
  • the low-density compositions of the invention include, at least in part, a non-porous or minimally porous, low-density material. Particulates formed from the low-density compositions of the invention are especially useful as cores for enzyme granules (e.g., marums, layered granules, prills, drum granules, agglomerated granules, or the like).
  • enzyme granules e.g., marums, layered granules, prills, drum granules, agglomerated granules, or the like.
  • compositions can further include one or more proteins, e.g., hydrolytic enzymes; and/or the compositions, or particulates formed therefrom, can be enrobed with such proteins.
  • proteins e.g., hydrolytic enzymes
  • the advantage in using the low-density material is that particulates, cores and granules with densities much lower than those achievable by prior methods can be produced. This can have a bearing on a number of applications, such as dispersion of a suspended particle in a liquid, flotation or buoyancy control of particles in specialized applications (i.e. chromatographic columns), segregation manipulation in powder applications, etc.
  • the term “density” refers to “true density,” “specific gravity” or “volumetric density,” as opposed to “bulk density” (unless otherwise stated).
  • the former can be determined, for example, by volume displacement using a liquid in which the particulates or granules do not dissolve (e.g., by way of mineral oil immersion).
  • a low-density composition of the present invention includes a non-porous or minimally porous (e.g., less than 0.25 by water vapor porosity test; preferably less than 0.20; most preferably less than 0.10), low-density material, e.g., hollowspheres, low-density minerals, low-density wood materials, or any combination thereof, and a binder material.
  • low-density material e.g., hollowspheres, low-density minerals, low-density wood materials, or any combination thereof
  • one or more proteins such as an enzyme, can further be included in the low-density composition.
  • the composition can be configured, for example, as a particulate. Where the particulates are intended for use in liquid wash solutions, they are preferably adapted to be readily soluble or dispersable in the wash liquor.
  • such particulates can be used as cores, upon which one or more layers can be applied.
  • one or more of the following layers can be applied to a particulate, or core, of the present invention: (i) an enzyme layer surrounding the core (especially where non-enzyme containing particulates are utilized); (ii) optionally, a barrier layer for guarding the enzyme(s) against potentially inactivating substances and/or preventing enzyme leakage; and (iii) an outermost layer, e.g., a protective or aesthetic overcoat.
  • the outermost layer provides a barrier to the harsh detergent elements as well as gives the desired aesthetic properties to the granule.
  • the non-porous or minimally porous, low-density material amount is preferably about 1-20% (w/w, relative to the weight of the granule); the enzyme amount is preferably about 0.5-30% (w/w, relative to the weight of the granule); and the outer coating amount is preferably about 1-50% (w/w, relative to the weight of the granule).
  • the low-density material is non-porous or minimally porous in water, substantially non-reactive, and has a low bulk density (e.g., less than 1 g/ml, and preferably no greater than 0.6 g/ml).
  • the non-porous or minimally porous, low-density material is selected from the group consisting of hollowspheres (e.g. hollosphere available commercially under the tradename Q-cel, from PQ Corporation), aluminum palmitate, aluminum tristearate, lithium borohydride, potassium borohydride, saw dust (e.g. balsa wood), milled corncob, aerogel shards, hollow fibers (e.g. Dacron (DuPont)), and low-density forms of silicon dioxide (such as used as flow aids for powders).
  • hollowspheres e.g. hollosphere available commercially under the tradename Q-cel, from PQ Corporation
  • aluminum palmitate aluminum tristearate
  • lithium borohydride potassium borohydride
  • the low-density composition of the invention is formed into a particulate, or core, about a small seed or carrier particle.
  • a seed or carrier particle is an inert particle upon which the low-density material (along with a binder and, optionally, one or enzymes) can be deposited (e.g., coated, layered, etc.).
  • Suitable seed particles include inorganic salts, sugars, sugar alcohols, small organic molecules such as organic acids or salts, minerals such as clays or silicates or a combination of two or more of these.
  • Suitable soluble ingredients for incorporation into seed particles include sodium chloride, potassium chloride, ammonium sulfate, sodium sulfate, sodium sesquicarbonate, urea, citric acid, citrate, sorbitol, mannitol, oleate, sucrose, lactose and the like. Soluble ingredients can be combined with dispersible ingredients such as talc, kaolin or bentonite. Seed particles can be fabricated by a variety of granulation techniques including: crystallization, precipitation, pan-coating, fluid-bed coating, fluid-bed agglomeration, rotary atomization, extrusion, prilling, spheronization, drum granulation and/or high shear agglomeration.
  • the ratio of seed particles to particulates is 1:1.
  • the ratio of cores to granules is also 1:1.
  • the seed particle delivers acceptable strength while not adversely affecting the density of the final core or granule.
  • Suitable binders include common yellow dent starch, modified starches (e.g., hydroxypropyl addition, ethoxylation, acetylation, acid thinning etc.), sugars (e.g., sucrose, dextrose, fructose, lactose etc.), maltodextrin, polyvinylpyrolidine (PVP), polyethylene glycol (PEG), xanthum gum, gum arabic, acacia gum, alginate, carageenan, waxes (e.g., carnuba, beeswax, paraffin and blends thereof), high melting point surfactants (e.g., mp between 40 and 80°C).
  • modified starches e.g., hydroxypropyl addition, ethoxylation, acetylation, acid thinning etc.
  • sugars e.g., sucrose, dextrose, fructose, lactose etc.
  • maltodextrin e.g.
  • Proteins that are within the scope of the present invention include pharmaceutically important proteins such as hormones or other therapeutic proteins and industrially important proteins such as enzymes.
  • any enzyme or combination of enzymes may be used in the present invention.
  • Preferred enzymes include those enzymes capable of hydrolyzing substrates, e.g. stains. These enzymes, which are known as hydrolases, include, but are not limited to, proteases (bacterial, fungal, acid, neutral or alkaline), amylases (alpha or beta), lipases, cellulases and mixtures thereof. Particularly preferred enzymes are subtilisins and cellulases. Exemplary subtilisins are described in U.S. Patent 4,760,025, EP Patent 130 756 B1 and PCT Application WO 91/06637. Exemplary cellulases include Multifect L250TM and PuradaxTM, commercially available from Genencor International. Other enzymes that can be used in the present invention include oxidases, transferases, dehydratases, reductases, hemicellulases and isomerases.
  • the enzyme can be loaded include: centrally within the low-density material (e.g., in a layer around a centrally located seed particle); intermixed (e.g., homogeneously) with the low-density material; as a layer over, or surrounding, the low-density material; as a layer separated from the low-density material by one or more other layers; as well as any combination thereof.
  • Suitable plasticizers useful in the present invention include polyols such as glycerol, propylene glycol, polyethylene glycol (e.g., low MW PEGs), urea, or other known plasticizers.
  • Suitable anti-agglomeration agents include fine insoluble or sparingly soluble materials such as talc, TiO 2 , clays, amorphous silica, magnesium stearate, stearic acid and calcium carbonate. Plasticizers and anti-agglomeration agents can be included, for example, in an overcoating applied to a granule.
  • a barrier layer can be used to slow or prevent the diffusion of substances that can adversely affect the protein or enzyme in the granule.
  • the barrier layer can be made up of a barrier material and can be coated over the core and/or over an enzyme layer that surrounds the core; and/or the barrier material can be included in the core.
  • Suitable barrier materials include, for example, starch, inorganic salts or organic acids or salts.
  • the barrier layer comprises starch and a binder (e.g., sucrose) coated over a enzyme-containing or carrying, low-density core.
  • the granules of the present invention can comprise one or more coating layers.
  • coating layers may be one or more intermediate coating layers or such coating layers may be one or more outside coating layers or a combination thereof.
  • Coating layers may serve any of a number of functions in a granule composition, depending on the end use of the enzyme granule.
  • coatings may render the enzyme resistant to oxidation by bleach, prevent enzyme leakage, bring about the desirable rates of dissolution upon introduction of the granule into an aqueous medium, or provide a barrier against ambient moisture in order to enhance the storage stability of the enzyme and reduce the possibility of microbial growth within the granule.
  • Suitable coatings include water soluble or water dispersible film-forming polymers such as polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), cellulose derivatives such as methylcellulose (MC), hydroxypropyl methylcellulose (HPMC), hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, polyethylene glycol, polyethylene oxide, gum arabic, xanthan, carrageenan, chitosan, latex polymers, and enteric coatings.
  • PVA polyvinyl alcohol
  • PVP polyvinyl pyrrolidone
  • MC methylcellulose
  • HPMC hydroxypropyl methylcellulose
  • hydroxyethyl cellulose carboxymethyl cellulose
  • hydroxypropyl cellulose polyethylene glycol
  • polyethylene oxide gum arabic, xanthan, carrageenan, chitosan, latex polymers
  • enteric coatings may be used in conjunction with other active agents of the same or different categories.
  • Suitable PVAs for incorporation in the coating layer(s) of the granule include partially hydrolyzed, fully hydrolyzed and intermediately hydrolyzed PVAs having low to high degrees of viscosity.
  • the outer coating layer comprises partially hydrolyzed PVA having low viscosity.
  • Other vinyl polymers which may be useful include polyvinyl acetate and polyvinyl pyrrolidone.
  • Useful copolymers include, for example, PVA-methylmethacrylate copolymer and PVP-PVA copolymer and enteric co-polymers such as those sold under the tradename Eudragit® (Rhone Poulenc).
  • the coating layers of the present invention may further comprise one or more of the following: plasticizers, extenders, lubricants, pigments, and optionally additional enzymes.
  • plasticizers useful in the coating layers of the present invention are plasticizers including, for example, polyols such as sugars, sugar alcohols, or polyethylene glycols (PEGs), urea, glycol, propylene glycol or other known plasticizers such as triethyl citrate, dibutyl or dimethyl phthalate or water.
  • Suitable pigments useful in the coating layers of the present invention include, but are not limited to, finely divided whiteners such as titanium dioxide or calcium carbonate or colored pigments and dyes or a combination thereof. Preferably such pigments are low residue pigments upon dissolution.
  • Suitable extenders include sugars such as sucrose or starch hydrolysates such as maltodextrin and corn syrup solids, clays such as kaolin and bentonite and talc.
  • Suitable lubricants include nonionic surfactants such as Neodol, tallow alcohols, fatty acids, fatty acid salts such as magnesium stearate and fatty acid esters.
  • Adjunct ingredients may be added to the enzyme granules of the present invention.
  • Adjunct ingredients may include: metallic salts; solubilizers; activators; antioxidants; dyes; inhibitors; binders; fragrances; enzyme protecting agents/scavengers such as ammonium sulfate, ammonium citrate, urea, guanidine hydrochloride, guanidine carbonate, guanidine sulfamate, thiourea dioxide, monoethanolamine, diethanolamine, triethanolamine, amino acids such as glycine, sodium glutamate and the like, proteins such as bovine serum albumin, casein; surfactants including anionic surfactants, ampholytic surfactants, nonionic surfactants, cationic surfactants and long-chain fatty acid salts; builders; alkalis or inorganic electrolytes; bleaching agents; bluing agents and fluorescent dyes and whiteners; enzyme stabilizers such as betaine, peptides and caking inhibitors.
  • the granules produced in accordance with the present invention are roughly round, or spherical, in shape.
  • the true, or volumetric, density of the granules can be measured by methods well known in the art, such as by volume displacement using a liquid in which the granules do not dissolve (e.g., mineral oil immersion).
  • the granules produced according to the teachings herein have a true density of between 0.95-1.4 g/cm 3 ; more preferably between about 0.95-1.2 g/cm 3 ; and most preferably between about 1-1.15 g/cm 3 .
  • the granules of the present invention may be particularly useful in connection with liquid detergents.
  • the granules are dispersed and suspended within a liquid detergent having a water content of greater than 50%, and preferably at least about 60%.
  • the granules have a retained activity in storage for 3 weeks, at 35°C in such a liquid detergent of at least 50%, and preferably at least 60%, and most preferably at least 70% (e.g., 85% or greater).
  • the granules have a retained activity in storage for 4 weeks, at 37°C in such a liquid detergent of at least 50%, and preferably at least 60%, and most preferably at least 70% (e.g., 85% or greater).
  • the granules have a retained activity in storage under ambient, or normal, storage conditions for 6 months in such a liquid detergent of at least 50%, and preferably at least 60%, and most preferably at least 70% (e.g., 85% or greater).
  • the granules described herein may be made by methods known to those skilled in the art of particle generation, including but not limited to marumerization, drum granulation, fluid-bed spray-coating, pan-coating, or other suitable process, or combinations of such techniques.
  • marumerization drum granulation
  • fluid-bed spray-coating pan-coating
  • pan-coating pan-coating
  • a seed particle is charged into a fluid bed coater and fluidized.
  • a coating solution consisting of a binder or binder system along with a non-porous or minimally porous, low-density material (e.g., hollowspheres) and optionally including other low-density materials is sprayed onto the seed to generate a low density particulate, or core.
  • the non-porous or minimally porous, low-density material may be added dry along with application of a binder spray in either a pan or fluidized bed coater.
  • an enzyme can be layered onto the core.
  • this may be followed by other layers whose purpose can be, for example, buffering, providing a protective barrier, bulking, providing another value/performance added material.
  • a cosmetic coating can be applied to provide aesthetics and protection from the environment. If desired, the entire process can be performed in a pan coater. Moreover, any part of this process can be performed in either a pan coater or a fluidized bed coater.
  • Suitable seed particles for use in the just-described method include, for example, a sugar crystal, salt crystal, non-pareil, a prill with an acceptable melting point, an extruded particulate, a particulate from a drum granulation, etc.
  • a non-porous or minimally porous, low-density material e.g., hollowspheres
  • a solution consisting of melted components and little or no water or other solvent.
  • This solution can be fed to a spinning disc, centrifugal nozzle or any other type of prilling device which is used to generate spherical particles of sizes between 50 and 3000 ⁇ m.
  • the prills are generated at some height above a collection area which allows them to cool and harden as they fall.
  • a counter-current chilling air-stream may be used to facilitate prill hardening and control particle velocities.
  • enzyme may be added to the hot-melt solution in the form of a dry powder, enzyme-crystal slurry or paste, enzyme precipitate slurry or paste or in a solubilized form in either an aqueous or non-aqueous solvent.
  • solvent of liquid carrier concentration in the hot-melt cannot rise to above a level where spheroidal, non-friable prills are no longer formed. These enzyme prills can then be cosmetically coated, as an option.
  • low-density enzyme granules of the present invention are made by an extrusion method by adding the non-porous or minimally porous, low-density material (e.g., hollowspheres) to the dry blend and then processing as described in, for example, U.S. Patent No. 5,739,091.
  • non-porous or minimally porous, low-density material e.g., hollowspheres
  • low-density enzyme granules of the present invention are made by a drum granulation method by adding the non-porous or minimally porous, low-density material (e.g., hollowspheres) to the dry blend and processing as described in, for example, in PCT WO 90/09440.
  • non-porous or minimally porous, low-density material e.g., hollowspheres
  • the non-porous or minimally porous, low-density material can be blended into a solution/slurry that is used to produce the core of a microencapsulated product.
  • This solution can be sprayed along with a shell solution through a binary phase nozzle, where the core solution exits through the inner liquid,port and the shell solution exits through the outer concentric liquid port, and atomized via centrifugal force, mechanical vibration, jet cutting, sonics, cross shear from a liquid or gas stream, electromagnetic field, etc.
  • the microencapsulate can be collected in a liquid based collection bath, a solid media that facilitates free-flow of the product or in static or countercurrent air stream that allows hardening/setting up of the product before it reaches a collection vessel.
  • the microencapsulate can be dried and/or cosmetically coated.
  • the shell can be composed of any material(s) that efficiently entrap the inner core and provide enough rigidity so that the microcapsule can be handled in relevant applications without significantly deforming, agglomerating, decomposing or in other ways becoming non-utile.
  • 35 Kgs of the pan-coated low-density cores were loaded into a deseret-60 fluid bed coater and fluidized.
  • 65.8 Kgs of a solution containing 7.3% active alkaline protease and 2.1% polyvinylpyrolidine (Luviskol K-17 from BASF) was spray-coated onto the cores.
  • a 40% solids solution containing 4.8 Kg of dry corn starch, 2.118 Kgs of sucrose and 0.142 Kgs of hydrated starch was spray-coated onto the enzyme particulates.
  • Step Outlet Temperature C
  • Fluidized Air Flow CFM
  • Atomization Pressure PSI
  • sucrose seeds 7.81 Kgs of sucrose seeds, sieved between 35 to 50 standard mesh, were charged into a Glatt GPCG-30 fluidized bed coater, and fluidized with a fluidizing air stream of warm air.
  • granules of the present invention preferably exhibit no more than about 50% loss in activity over 4 weeks storage at 37°C in detergent and cleaning agents (e.g., dish detergents, laundry detergents, and hot surface cleaning solutions). More preferably, the granules taught herein have a minimum of 70% activity remaining after 4 weeks at 37C°. More preferably still, the granules taught herein have a minimum of 85% activity remaining after 4 weeks at 37C°. In tests carried out in support of the present invention, the granules of Example 1 exhibited nearly 85% activity remaining after 4 weeks at 37°C.
  • detergent and cleaning agents e.g., dish detergents, laundry detergents, and hot surface cleaning solutions. More preferably, the granules taught herein have a minimum of 70% activity remaining after 4 weeks at 37C°. More preferably still, the granules taught herein have a minimum of 85% activity remaining after 4 weeks at 37C°. In tests carried out in support of the present invention, the granules of Example 1
  • the elutriation test simulates the removal of surface dust be gentle pouring and fluidizing actions; the Heubach test is a more severe simulation of the crushing forces commonly encountered in industrial powder mixing, conveying, and sieving operations. Additional details of these tests can be found, for example, in "Enzymes In Detergency,” ed. Jan H. van Ee, et al., Chpt. 15, pgs. 310-312 (Marcel Dekker, Inc., New York, NY (1997)), and references cited therein.
  • Granules of the present invention preferably exhibit a dust figure of less than 1 ug/g (active dust) as determined by the elutriation attrition test.
  • Exemplary granules that have been tested in support of the present invention exhibit a dust figure of no greater than 1 ug/g.
  • a commonly used method for measuring enzyme release from a granule under typical liquid applications conditions is the enzyme dissolution test.
  • granules are added to a liquor that is chemically equivalent to the application conditions.
  • the test liquor can be set at differing temperatures to test for different application temperatures.
  • the granule containing liquor is agitated under conditions that are similar to application conditions, and samples of particulate-free liquor are removed with a filtered syringe at various times.
  • the samples are then assayed for enzyme activity (e.g., for proteases, by way of a standard assay involving the hydrolysis of casein substrate).
  • Granules of the present invention preferably have at least 80%, and preferably at least 90%, of the enzyme activity released into the liquor within 5 minutes at 15°C. More preferably, the granules taught herein have a minimum of 90% of the enzyme activity released into the liquor within 3 minutes at 15°C. Exemplary granules that have been tested in support of the present invention exhibit an enzyme release rate of no less than 90% in 5 minutes at 15°C, and most exhibit an enzyme release rate of no less than 90% in 3 minutes at 15°C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Genetics & Genomics (AREA)
  • Zoology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Health & Medical Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Microbiology (AREA)
  • Biotechnology (AREA)
  • Biochemistry (AREA)
  • Biomedical Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
  • Enzymes And Modification Thereof (AREA)
  • Glanulating (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP00903190A 1999-01-08 2000-01-07 Low-density compositions and particulates including same Revoked EP1149151B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US11525599P 1999-01-08 1999-01-08
US115255P 1999-01-08
PCT/US2000/000464 WO2000040689A2 (en) 1999-01-08 2000-01-07 Low-density compositions and particulates including same

Publications (2)

Publication Number Publication Date
EP1149151A2 EP1149151A2 (en) 2001-10-31
EP1149151B1 true EP1149151B1 (en) 2006-03-29

Family

ID=22360201

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00903190A Revoked EP1149151B1 (en) 1999-01-08 2000-01-07 Low-density compositions and particulates including same

Country Status (13)

Country Link
US (2) US6534466B2 (enExample)
EP (1) EP1149151B1 (enExample)
JP (1) JP2002534076A (enExample)
CN (1) CN1336954A (enExample)
AT (1) ATE321838T1 (enExample)
AU (1) AU2497100A (enExample)
CA (1) CA2354529A1 (enExample)
DE (1) DE60026970T2 (enExample)
DK (1) DK1149151T3 (enExample)
ES (1) ES2257999T3 (enExample)
HK (1) HK1044017A1 (enExample)
MX (1) MXPA01006944A (enExample)
WO (1) WO2000040689A2 (enExample)

Families Citing this family (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR0007954A (pt) * 1999-02-02 2001-11-06 Procter & Gamble Granulados enzimáticos de baixa densidade e composições empregando os mesmos
EP1490485B1 (en) * 2002-03-27 2015-03-04 Novozymes A/S Granules with filamentous coatings
US7419947B2 (en) * 2002-03-27 2008-09-02 Novozymes A/S Process for preparing granules with filamentous coatings
FR2864962B1 (fr) * 2004-01-08 2007-09-14 Seppic Sa Nouveaux granules filmogenes poreux, procede pour leur preparation et application dans le pelliculage des comprimes et confiseries
US7531365B2 (en) * 2004-01-08 2009-05-12 International Flavors & Fragrances Inc. Analysis of the headspace proximate a substrate surface containing fragrance-containing microcapsules
CN101068912A (zh) * 2004-11-30 2007-11-07 株式会社Lg生活健康 改善衣物触感的洗衣洗涤剂组合物及其制备方法
EP1912194B1 (en) * 2005-07-20 2013-11-20 Nissin Dental Products, Inc. Multilayered model tooth for dental training
DE202006021153U1 (de) 2005-10-12 2013-02-22 Danisco Us Inc. Stabile, haltbare Granulate mit aktiven Mitteln
US8496966B2 (en) * 2005-10-24 2013-07-30 Cycle Group, Inc. Quick dissolving carrier granules
CN101636480B (zh) * 2007-01-11 2014-04-09 诺维信公司 包含活性化合物的颗粒
KR101392380B1 (ko) * 2007-02-21 2014-05-07 주식회사 엘지생활건강 산성형태의 수용성 고분자를 함유하는 분말세제 입자 및그의 제조방법
AU2008251642B2 (en) * 2007-05-10 2014-02-13 Danisco Us Inc., Genencor Division Stable enzymatic peracid generating systems
KR20100123694A (ko) 2008-02-14 2010-11-24 다니스코 유에스 인크. 소형 효소-함유 과립
WO2011090980A1 (en) 2010-01-20 2011-07-28 Danisco Us Inc. Mold treatment
EP2596093B1 (en) * 2010-07-20 2017-12-13 The Procter and Gamble Company Delivery particles with a plurality of cores
CN102433225B (zh) * 2011-12-29 2013-02-20 青岛蔚蓝生物集团有限公司 一种碱性蛋白酶包衣微丸及其制备方法
US9894917B2 (en) 2012-02-07 2018-02-20 Danisco Us Inc Glycosylation as a stabilizer for phytase
AU2013217566B2 (en) 2012-02-07 2016-11-17 Danisco Us Inc. Improvement of stability of phytase with phytic acid, and compositions comprising phytase and phytic acid
US20130284637A1 (en) 2012-04-30 2013-10-31 Danisco Us Inc. Unit-dose format perhydrolase systems
EP2863758B1 (en) 2012-06-20 2019-11-06 Danisco US Inc. Sandwich granule
EP2874506B1 (en) 2012-07-18 2019-04-10 Danisco US Inc. Method of making enzyme granules
WO2015057619A1 (en) 2013-10-15 2015-04-23 Danisco Us Inc. Clay granule
EP3068879B1 (en) 2013-11-14 2019-12-25 Danisco US Inc. Stable enzymes by glycation reduction
FR3025052B1 (fr) * 2014-08-19 2017-12-15 Isorg Dispositif de detection d'un rayonnement electromagnetique en materiaux organiques
CN104479909B (zh) * 2014-12-01 2017-07-21 湖南新鸿鹰生物工程有限公司 一种含真菌α‑淀粉酶的洗涤复合酶及其制备方法
DK3270893T3 (da) 2015-03-19 2021-11-01 Danisco Us Inc Stabile granulater med lav indre vandaktivitet
WO2016201069A1 (en) * 2015-06-09 2016-12-15 Danisco Us Inc Low-density enzyme-containing particles
BR112020009093A2 (pt) 2017-11-09 2020-10-13 Basf Se partícula de enzima, composições de lavagem ou limpeza e de alimento ou ração, e, uso de um pigmento branco orgânico
MX2020011305A (es) 2018-04-26 2021-01-08 Danisco Us Inc Método para aumentar la estabilidad de una fitasa en una composición sólida y una composición granulada que comprende fosfato y fitasa.
NL2021893B1 (en) 2018-10-26 2020-05-13 Citeq B V Biological pest control agent
BR112022000351A2 (pt) 2019-07-09 2022-05-10 Dupont Nutrition Biosci Aps Composições de enzima particuladas revestidas de gordura
WO2021086605A1 (en) 2019-10-28 2021-05-06 Danisco Us Inc Methods and compositions for remediating cyanuric acid in aqueous liquids
CN111701545B (zh) * 2020-06-04 2022-03-25 上海工程技术大学 一种适用于生产微胶囊型土壤调理剂的滴丸生产系统
WO2023019073A1 (en) * 2021-08-13 2023-02-16 Ppg Industries Ohio, Inc. Coating compositions, methods for using them and systems that include them

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1590432A (en) 1976-07-07 1981-06-03 Novo Industri As Process for the production of an enzyme granulate and the enzyme granuate thus produced
JPS57188435A (en) 1981-05-14 1982-11-19 Meisei Shokai:Kk Manufacture of colored fine hollow sphere
NZ208612A (en) 1983-06-24 1991-09-25 Genentech Inc Method of producing "procaryotic carbonyl hydrolases" containing predetermined, site specific mutations
US4760025A (en) 1984-05-29 1988-07-26 Genencor, Inc. Modified enzymes and methods for making same
US5185258A (en) 1984-05-29 1993-02-09 Genencor International, Inc. Subtilisin mutants
JPS6192570A (ja) 1984-10-12 1986-05-10 Showa Denko Kk 酵素造粒法
US4689297A (en) 1985-03-05 1987-08-25 Miles Laboratories, Inc. Dust free particulate enzyme formulation
US4828723A (en) * 1987-07-15 1989-05-09 Colgate-Palmolive Company Stable non-aqueous suspension containing organophilic clay and low density filler
US4931195A (en) * 1987-07-15 1990-06-05 Colgate-Palmolive Company Low viscosity stable non-aqueous suspension containing organophilic clay and low density filler
DK435687D0 (da) * 1987-08-21 1987-08-21 Novo Industri As Enzymholdigt granulat og fremgangsmaade til fremstilling deraf
FR2618157B1 (fr) 1988-07-15 1994-01-21 Colgate Palmolive Cy Suspension non aqueuse stable contenant une argile organophile et une charge a basse densite
DK78189D0 (da) * 1989-02-20 1989-02-20 Novo Industri As Enzymholdigt granulat og fremgangsmaade til fremstilling deraf
ATE94206T1 (de) 1989-12-21 1993-09-15 Novo Nordisk As Enzymhaltige zubereitung und eine solche zubereitung enthaltendes detergens.
US5814501A (en) 1990-06-04 1998-09-29 Genencor International, Inc. Process for making dust-free enzyme-containing particles from an enzyme-containing fermentation broth
US5324649A (en) * 1991-10-07 1994-06-28 Genencor International, Inc. Enzyme-containing granules coated with hydrolyzed polyvinyl alcohol or copolymer thereof
ES2167319T3 (es) * 1991-10-07 2002-05-16 Genencor Int Granulo que contiene una enzima revestida.
EP0620848A4 (en) * 1991-10-10 1996-06-12 Genencor Int PROCESS FOR THE MANUFACTURE OF DUST-FREE ENZYMES.
ATE161045T1 (de) * 1992-08-14 1997-12-15 Genencor Int Gmbh Neue enzymgranulate
DE4322229A1 (de) * 1993-07-05 1995-01-12 Cognis Bio Umwelt Umhüllte Enzymzubereitung für Wasch- und Reinigungsmittel
DE4329463A1 (de) * 1993-09-01 1995-03-02 Cognis Bio Umwelt Mehrenzymgranulate
AU718010B2 (en) 1995-10-06 2000-04-06 Genencor International, Inc. Microgranule for food/feed applications
US5668099A (en) * 1996-02-14 1997-09-16 The Procter & Gamble Company Process for making a low density detergent composition by agglomeration with an inorganic double salt
DE19619221A1 (de) * 1996-05-13 1997-11-20 Solvay Enzymes Gmbh & Co Kg Enzymgranulat für Wasch- und Reinigungsanwendungen
BR9810633A (pt) * 1997-06-27 2000-10-03 Procter & Gamble Composições de detergente lìquido não aquoso contendo partìculas enzimáticas tendo densidade reduzida
CN1242060C (zh) 1997-12-20 2006-02-15 金克克国际有限公司 基体颗粒
US6423517B2 (en) 1997-12-20 2002-07-23 Genecor International, Inc. Granule containing protein and salt layered on an inert particle
KR20010033321A (ko) 1997-12-20 2001-04-25 마가렛 에이.혼 수화된 차단 재료를 가지는 과립
DK1129163T3 (da) * 1998-11-13 2011-03-21 Danisco Us Inc Granulat med lav massefylde i fluidiseret lag

Also Published As

Publication number Publication date
WO2000040689A3 (en) 2000-11-30
MXPA01006944A (es) 2003-09-10
DE60026970D1 (de) 2006-05-18
AU2497100A (en) 2000-07-24
HK1044017A1 (zh) 2002-10-04
EP1149151A2 (en) 2001-10-31
WO2000040689A2 (en) 2000-07-13
US20020082183A1 (en) 2002-06-27
ATE321838T1 (de) 2006-04-15
CN1336954A (zh) 2002-02-20
ES2257999T3 (es) 2006-08-16
US6534466B2 (en) 2003-03-18
JP2002534076A (ja) 2002-10-15
CA2354529A1 (en) 2000-07-13
US6583099B2 (en) 2003-06-24
DK1149151T3 (da) 2006-07-31
US20020193275A1 (en) 2002-12-19
DE60026970T2 (de) 2006-11-30

Similar Documents

Publication Publication Date Title
EP1149151B1 (en) Low-density compositions and particulates including same
US6635611B2 (en) Fluidized bed low density granule
US8535924B2 (en) Granules with reduced dust potential comprising an antifoam agent
EP1037968B1 (en) Matrix granule
KR20010033321A (ko) 수화된 차단 재료를 가지는 과립
JP2003514922A (ja) 蛋白質含有顆粒および顆粒配合物
US20010056177A1 (en) Matrix granule
CA2443112C (en) Granule with reduced dust potential
MXPA00005830A (en) Granule with hydrated barrier material
MXPA00005831A (en) Matrix granule

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20010629

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17Q First examination report despatched

Effective date: 20031128

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20060329

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060329

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060329

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060329

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60026970

Country of ref document: DE

Date of ref document: 20060518

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060629

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2257999

Country of ref document: ES

Kind code of ref document: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060829

ET Fr: translation filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070108

26 Opposition filed

Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN VTP (PATEN

Effective date: 20061221

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070131

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20070220

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20070322

Year of fee payment: 8

NLR1 Nl: opposition has been filed with the epo

Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN VTP (PATEN

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 20071025

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Free format text: 20071025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060630

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20080115

Year of fee payment: 9

Ref country code: FR

Payment date: 20070109

Year of fee payment: 8

NLR2 Nl: decision of opposition

Effective date: 20071025

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20080104

Year of fee payment: 9

Ref country code: FI

Payment date: 20080115

Year of fee payment: 9

Ref country code: GB

Payment date: 20080102

Year of fee payment: 9

Ref country code: IT

Payment date: 20080129

Year of fee payment: 9

Ref country code: NL

Payment date: 20080103

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060329

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070107